Compositions and Methods For Plugging Honeycomb Bodies With Reduced Plug Depth Variability

ABSTRACT

A composition for applying to a honeycomb body includes a refractory filler, an organic binder, an inorganic binder, and a liquid vehicle, wherein the refractory filler, the particle size distribution of the refractory filler, the organic binder, and the inorganic binder are selected such that, when the composition is applied to plug a plurality of channels of the honeycomb body, the plug depth variability is reduced.

CROSS REFERENCE TO RELATED APPLICATION

This application is a Continuation-in-Part of U.S. patent applicationSer. No. 13/599,584, filed on Aug. 30, 2012, which is herebyincorporated by reference for all purposes as if fully set forth herein.

BACKGROUND

The disclosure relates generally to porous honeycomb ceramics and moreparticularly to improved compositions that can be applied to poroushoneycomb ceramics.

Ceramic wall flow filters are finding widening use for the removal ofparticulate pollutants from diesel or other combustion engine exhauststreams. A number of different approaches for manufacturing such filtersfrom channeled honeycomb structures formed of porous ceramics are known.The most widespread approach is to position cured plugs of sealingmaterial at the ends of alternate channels of such structures, which canblock direct fluid flow through the channels and force the fluid streamthrough the porous channel walls of the honeycombs before exiting thefilter.

Important aspects of plugging honeycomb structures include plug depthand plug quality. Plug quality is often correlated to the presence ofvoids in the plugs. In general, the presence of voids can be reduced byreducing the amount of water in the plugging composition and/orincreasing the particle size of certain batch components in the pluggingcomposition. However, such modifications can lead to plugs withinsufficient depth and, hence, insufficient mechanical (or “push out”)strength.

On the other hand, shorter plugs provide less back pressure, higherfilter volume for the same external geometry, thus reducing thefrequency of regenerations and improving fuel economy. Moreover, shorterplugs provide better material utilization, thereby reducing filtermanufacturing costs. Accordingly, it is desirable to provide plugs thatare as short as possible while still having the requisite depth toprovide sufficient mechanical (or “push out”) strength.

A challenge for simultaneously addressing all of these considerationsinvolves plug depth variability. Plug depth variability is typicallydriven by differences in the flow rate of a plugging composition indifferent filter channels. Plugs in channels where there is relativelymore resistance to flow tend to be shorter whereas plugs in channelswhere there is relatively less resistance to flow tend to be longer.Such variability can result in at least some relatively shorter plugsfailing to provide requisite mechanical strength. Accordingly, given theever increasing need to provide for shorter plugs, there simultaneouslyexists a need to provide for reduced plug depth variability in order tominimize the incidence of plugs that fail to provide requisitemechanical strength.

SUMMARY

One embodiment of the disclosure relates to a composition for applyingto a honeycomb body having a plurality of parallel channels. Thecomposition includes a refractory filler having a particle sizedistribution. The composition also includes an organic binder, aninorganic binder, and a liquid vehicle. The refractory filler, theparticle size distribution of the refractory filler, the organic binder,and the inorganic binder are selected such that, when the composition isapplied to plug a plurality of channels of the honeycomb body, aplurality of plugs formed therefrom have an average plug depth and adepth range, such that for channels of a given cross-sectional size, thedepth range is less than 30% of the average plug depth.

Another embodiment of the disclosure relates to a porous ceramichoneycomb body comprising a plurality of parallel channels bounded byporous ceramic channel walls. Selected channels incorporate plugspermanently sealed to the channel walls. The plugs include a refractoryfiller having a particle size distribution and an inorganic binder. Therefractory filler, the particle size distribution of the refractoryfiller, and the inorganic binder are selected such that the plugs havean average plug depth and a depth range, such that for channels of agiven cross-sectional size, the depth range is less than 30% of theaverage plug depth.

Yet another embodiment of the disclosure relates to a method forapplying a plugging composition to a honeycomb body having a pluralityof parallel channels. The method includes applying a composition to thehoneycomb body. The composition includes a refractory filler having aparticle size distribution. The composition also includes an organicbinder, an inorganic binder, and a liquid vehicle. The refractoryfiller, the particle size distribution of the refractory filler, theorganic binder, and the inorganic binder are selected such that, whenthe composition is applied to plug a plurality of channels of thehoneycomb body, a plurality of plugs formed therefrom have an averageplug depth and a depth range, such that for channels of a givencross-sectional size, the depth range is less than 30% of the averageplug depth.

Additional features and advantages will be set forth in the detaileddescription which follows, and in part will be readily apparent to thoseskilled in the art from the description or recognized by practicing theembodiments as described in the written description and claims hereof,as well as the appended drawings.

Exemplary embodiments of the present disclosure provide a compositionfor applying to a honeycomb body having a plurality of parallelchannels. The composition includes a refractory filler having a particlesize distribution. The composition also includes an organic binder, aninorganic binder, and a liquid vehicle. The inorganic binder comprises apolydisperse colloidal silica.

Exemplary embodiments of the present disclosure also provide a porousceramic honeycomb body comprising a plurality of parallel channelsbounded by porous ceramic channel walls. Selected channels incorporateplugs permanently sealed to the channel walls. The plugs include arefractory filler having a particle size distribution and an inorganicbinder. The inorganic binder comprises a polydisperse colloidal silica.

An exemplary embodiment of the present disclosure also provides a methodfor applying a plugging composition to a honeycomb body having aplurality of parallel channels. The method includes applying acomposition to the honeycomb body. The composition includes a refractoryfiller having a particle size distribution. The composition alsoincludes an organic binder, an inorganic binder, and a liquid vehicle.The inorganic binder comprises a polydisperse colloidal silica.

It is to be understood that both the foregoing general description andthe following detailed description are merely exemplary, and areintended to provide an overview or framework to understand the natureand character of the claims.

The accompanying drawings are included to provide a furtherunderstanding, and are incorporated in and constitute a part of thisspecification. The drawings illustrate one or more embodiment(s), andtogether with the description serve to explain principles and operationof the various embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 plots average plug depth and plug depth range for plugs appliedto a honeycomb structure according to a comparative pluggingcomposition.

FIG. 2 plots average plug depth and plug depth range for plugs appliedto a honeycomb structure according to an exemplary plugging composition.

FIG. 3 shows samples of plugs applied to a honeycomb structure accordingto an exemplary embodiment, calcined at 600° C. for 3 hrs, and crosssectioned.

FIG. 4 shows a microprobe analysis of a cross sectioned plug applied toa honeycomb structure according to an exemplary embodiment.

FIG. 5A shows a transmission electron microscopy image of a mono-modaldisperse colloidal silica with a particle size range d50 ofapproximately 12 nm. FIG. 5B shows a transmission electron microscopyimage of colloidal silica having a poly-disperse mixture of largerparticle size range d50 of approximately 70 nm and smaller particle sizerange d50 of approximately 12 nm.

FIGS. 6A and 6B are plots of particle size distribution (PSD) andsurface area for colloidal silica used in exemplary embodiments of thecomposition disclosed herein.

FIG. 7 shows a plot of plug depth of compositions according to exemplaryembodiments.

FIG. 8 shows a plot of air erosion testing of plugs applied to ahoneycomb structure according to an exemplary embodiment, calcined at600° C. for 3 hrs, and sectioned before testing.

FIG. 9 shows a plot of plug push out testing of plugs applied tohoneycomb structure according to exemplary embodiments.

FIG. 10 shows a microprobe silica scan of a cross sectioned plug appliedto a honeycomb structure according to an exemplary embodiment.

FIG. 11 shows a plot of plug density according to exemplary embodimentsof plug composition.

FIG. 12 shows sectioned samples of exemplary embodiments of plugcompositions applied to a honeycomb structure under hot air drying (HAD)and microwave drying (MW).

FIG. 13 shows cutback erosion results of exemplary embodiments.

FIG. 14 shows plug push out test results of exemplary embodiments.

DETAILED DESCRIPTION

Various embodiments of the disclosure will be described in detail withreference to the drawings.

As used herein, the term “average plug depth” refers to the total depth(or length) of all of the plugs in a given area (such as on one or moreend faces of a honeycomb body) divided by the number of plugs in thatarea.

As used herein, the term “depth range” refers to the difference in depthbetween the deepest (or longest) plug in a given area (such as on one ormore end faces of a honeycomb body) and the shallowest (or shortest)plug in that area.

As used herein, the term “channels of a given cross sectional size”refers to channels of a honeycomb body that have the same approximatecross sectional dimensions. For example, for a honeycomb body having ACTcell geometry as described in U.S. Pat. No. 6,696,132, channels of agiven cross sectional size could refer to the collective inlet cellchannels (shown as 14 in FIG. 3 of that patent) having a relativelylarger hydraulic diameter or to the collective outlet cell channels(shown as 16 in FIG. 3 of that patent) having a relative smallerhydraulic diameter.

As used herein, the term “push out strength” refers to the pressure (inbars, unless otherwise indicated) required to push a given plug out of agiven channel. Plug push out strength can be determined by eitherpushing a plug from the top (i.e., side closest to part end face) orbottom (i.e., side farthest from part end face). In either case, a loadcell is utilized to push a pin into the plug, wherein the pincross-sectional area is optimally about 70% of the cross section of theplugged cell. When pushed from the top, the force required to push thetooling 0.2 inches into the plug is recorded. When pushed from thebottom, the force required to break through the plug and remove it fromthe face is recorded. When pushing from the top, the tooling includesthree pins, one to push the plug and two for alignment. When pushingfrom the bottom, the cell walls provide guidance and only the pushingpin is needed.

As used herein, the term D₁₀ refers to a particle size wherein 90% ofthe particles in a distribution have a larger particle size and 10% ofthe particles in a distribution have a smaller particle size.

As used herein, the term D₉₀ refers to a particle size wherein 90% ofthe particles in a distribution have a smaller particle size and 10% ofthe particles in a distribution have a larger particle size.

As used herein, the term D₅₀ refers to a particle size where 50% of theparticles in a distribution have a smaller particle size and 50% of theparticles in a distribution have a larger particle size.

As used herein, the term “D factor” (D_(f))=(D₅₀−D₁₀)/D₅₀.

As used herein, the term “D breadth” (D_(breadth))=(D₉₀−D₁₀)/D₅₀.

Embodiments disclosed herein include compositions for applying to ahoneycomb body having a plurality of parallel channels, such ascompositions for plugging one or more channels of a honeycomb bodyhaving a plurality of parallel channels. The compositions include arefractory filler having a particle size distribution, an organicbinder, an inorganic binder, and a liquid vehicle. The refractoryfiller, the particle size distribution of the refractory filler, theorganic binder, and the inorganic binder are selected such that, whenthe composition is applied to plug a plurality of channels of thehoneycomb body, a plurality of plugs formed therefrom have an averageplug depth and a depth range, such that for channels of a givencross-sectional size, the depth range is less than 30% of the averageplug depth, such as less than 25% of the average plug depth, and furthersuch as less than 20% of the average plug depth, including between 10%and 30% of the average plug depth and further including between 15% and25% of the average plug depth.

In certain exemplary embodiments, the average plug depth is less than 7millimeters, such as less than 6 millimeters, and further such as lessthan 5 millimeters, including from 4 to 7 millimeters, and furtherincluding from 4 to 6 millimeters, and yet further including from 4 to 5millimeters. In such embodiments, the depth range of the plugs is lessthan 2.1 millimeters, such as less than 1.8 millimeters, and furthersuch as less than 1.5 millimeters, and still yet further such as lessthan 1.2 millimeters, and even still yet further such as less than 1.0millimeters, including between 0.5 and 2.1 millimeters, and furtherincluding between 0.5 and 1.5 millimeters, and yet further includingbetween 0.5 millimeters and 1.0 millimeters.

Embodiments disclosed herein can enable plugs meeting theabove-disclosed average plug depth and depth range parameters whereinall of the plurality of plugs in the channels have a push out strengthof at least 10 bar, such as at least 15 bar, and further such as atleast 20 bar, and still yet further such as at least 25 bar. Such plugscan have an average push out strength of at least 50 bar, such as atleast 60 bar, and further such as at least 70 bar, and still yet furthersuch as at least 80 bar.

The refractory filler can include at least one inorganic powder. Theinorganic powder may, for example, include a ceramic, i.e., pre-reactedor ceramed, refractory powder. In other embodiments, the powders can berefractory glass powders, or glass-ceramic powders. Still further, inother embodiments the inorganic powder batch mixture can comprise anycombination of two or more of the aforementioned refractory powders.Exemplary refractory powders may include cordierite, mullite, aluminumtitanate, silicon carbide, silicon nitride, calcium aluminate,beta-eucryptite, and beta-spodumene.

The particle size distribution of the refractory filler can fall withina predetermined specified range. In that regard, applicants havesurprisingly found that maintaining the particle size distribution ofthe refractory filler within a specified range, in combination withspecified combinations of organic and inorganic binders, can result inplugging compositions that enable reduced plug depth variability. Inparticular, applicants have found that by keeping the particle sizedistribution of the refractory filler within a specified range, incombination with specified combinations of organic and inorganicbinders, channels of a honeycomb body can be plugged with the resultingcomposition, wherein the flow of the composition into the channelsbecomes restricted due to syneresis. As the composition penetratesfurther into the channels, the velocity of the flow slows down andeventually stops. This allows plugging composition in slower flowingchannels to catch up to plugging composition in channels that initiallyflows faster. This phenomenon, thus, reduces the depth variability ofthe plugs.

Accordingly, in certain exemplary embodiments, the refractory fillerincludes at least one inorganic powder having a median particle size(D₅₀) of at least 15 microns, such as a median particle size (D₅₀) offrom 15 to 50 microns, and further such as a median particle size (D₅₀)of from 18 to 40 microns, and still further such as a median particlesize (D₅₀) of from 30 to 40 microns, and even further such as a medianparticle size (D₅₀) of from 30 to 35 microns.

In certain exemplary embodiments, the inorganic powder has a D₁₀ of atleast 4 microns, such as at least 6 microns, and further such as atleast 8 microns, and yet further such as at least 10 microns, includingfrom 4 to 16 microns, and further including from 8 to 14 microns, andstill further including from 10 to 12 microns.

In certain exemplary embodiments, the inorganic powder has a D₉₀ of atleast 55 microns, such as at least 65 microns, and further such as atleast 75 microns, and yet further such as at least 85 microns, includingfrom 55 to 120 microns, and further including from 75 to 110 microns,and still further including from 85 to 100 microns.

In certain exemplary embodiments, the inorganic powder has a medianparticle size (D₅₀) of from 15 to 50 microns, and further such as amedian particle size (D₅₀) of from 20 to 45 microns, and even furthersuch as a median particle size (D₅₀) of from 25 to 40 microns, and yeteven further such as a median particle size (D₅₀) of from 30 to 35microns, has a D₁₀ of from 4 to 16 microns, and further including from 8to 14 microns, and still further including from 10 to 12 microns, and aD₉₀ of from 55 to 120 microns, and further including from 75 to 110microns, and still further including from 85 to 100 microns.

For example, in one set of exemplary embodiments, the refractory fillercomprises aluminum titanate powder having a median particle size (D₅₀)of at least 15 microns, such as a median particle size of (D₅₀) of from15 to 50 microns, and further such as a median particle size (D₅₀) offrom 20 to 45 microns, and even further such as a median particle size(D₅₀) of from 25 to 40 microns, and yet even further such as a medianparticle size (D₅₀) of from 30 to 35 microns. In one set of exemplaryembodiments, the refractory filler comprises cordierite powder having amedian particle size (D₅₀) of at least 10 microns, such as a medianparticle size of (D₅₀) of from 15 to 50 microns, and further such as amedian particle size (D₅₀) of from 15 to 40 microns, and even furthersuch as a median particle size (D₅₀) of from 20 to 30 microns. In oneset of exemplary embodiments, the refractory filler comprises mullitepowder having a median particle size (D₅₀) of at least 15 microns, suchas a median particle size of (D₅₀) of from 15 to 50 microns, and furthersuch as a median particle size (D₅₀) of from 25 to 40 microns, and evenfurther such as a median particle size (D₅₀) of from 30 to 35 microns.

The compositions further comprise a binder component comprised of aninorganic binder. In some embodiments, the inorganic binder is a gelledinorganic binder such as gelled colloidal silica. Other embodiments ofan inorganic binder could include a non-gelled colloidal silica, apowdered silica, or a low-temperature glass. According to embodiments,the incorporation of a gelled inorganic binder may minimize or evenprevent the migration of the inorganic binder particles into microcracksof a honeycomb body on which the composition is applied. Accordingly, asused herein, the term “gelled inorganic binder” refers to a colloidaldispersion of solid inorganic particles in which the solid inorganicparticles form an interconnected network or matrix in combination with acontinuous fluid phase, resulting in a viscous semi-rigid material.Further, it should be understood that there can be relative levels ordegrees of gelation. To that end, since a colloidal dispersion cancomprise solid particles having particle sizes diameters less than 100nm, such as less than 50 nm, and further such as less than 25 nm, andstill further such as less than 15 nm, a gelled inorganic binder as usedherein comprises an interconnected network of the dispersed inorganicparticles that is sufficient to prevent at least a portion of theinorganic binder particles from migrating into microcracks of ahoneycomb structure upon which the composition containing the gelledinorganic binder has been applied.

The gelled inorganic binder may be pre-gelled prior to introducing theinorganic binder into the powder composition. Alternatively, in otherembodiments, the inorganic binder can be gelled after it has beencombined with one or more other components of the disclosedcompositions. For example, in embodiments of the disclosure, theinorganic binder component of the composition can initially comprise anon-gelled colloidal silica which is subsequently gelled after beingincorporated into the powdered batch composition. To that end,dispersed-phase inorganic particles within a colloid can be largelyaffected by the surface chemistry present in the colloid and, as such,in embodiments the gelation of a colloid can be effected by altering thesurface chemistry within the colloid.

Accordingly, the non-gelled colloidal silica can subsequently be gelledby the addition of one or more gelling agents to the composition. Inembodiments, colloidal silica may be gelled by increasing the ionconcentration of the composition. In other embodiments, colloidal silicacan be gelled by altering the pH of the composition. Still furtherembodiments can comprise both increasing the ion concentration andaltering the pH of the composition. It should be understood that thegelling agent can be used in any amount effective to provide a gelledinorganic binder as described herein.

Exemplary gelling agents that function to increase the ion concentrationof the disclosed composition, i.e., ion increasing gelling agents,include one or more water soluble salts. To that end, exemplary watersoluble salts that are suitable gelling agents include magnesium saltssuch as magnesium chloride, or magnesium acetate, calcium salts such ascalcium chloride, or even sodium salts such as sodium chloride. Stillfurther, in embodiments of the invention the use of salts comprising 2⁺cations, such as Mg and Ca, can be particularly effective to gel aninorganic binder component at relatively low salt concentrations.

As noted above, an inorganic binder such as colloidal silica can also begelled by altering the pH of the composition. To that end, the pH of thedisclosed compositions can be increased or decreased by the use of a pHadjusting gelling agent comprising an acid, a base, or with acombination of an acid and a base. Exemplary pH adjusting gelling agentsare acid gelling agents which include, without limitations hydrochloricacid, sulfuric acid, and nitric acid. In still another exemplaryembodiment, the acid gelling agent may include organic acids such ascitric acid, and acetic acid. Exemplary pH adjusting gelling agentcomprising base gelling agents include, without limitation, ammoniumhydroxide, sodium hydroxide, and triethanol amine (hereinafter “TEA”).

According to embodiments, increasing the ion concentration of thecomposition by the addition of a salt or salt solution can result innon-uniform gelation due to the non-uniform salt concentrationsthroughout the composition and particularly at or near the region wherethe ion increasing gelling agent was introduced. According to theseembodiments, a more uniform and controlled gelation may be achieved by acombination of one or more ion increasing gelling agents and one or morepH adjusting gelling agents. For example, the ion concentration of thecomposition can initially be increased within a first pH range having arelatively longer gel times. The pH of the composition can then beadjusted to a second pH range exhibiting relatively shorter gel times.Therefore, since some colloidal silica solutions exhibit a minimum geltime as a function of pH, local deviations in pH will not result in anysubstantially non-uniform gelations.

In embodiments of the disclosure, one exemplary combination of an ionincreasing gelling agent and a pH adjusting gelling agent comprises theuse of TEA as both a base and a salt in a colloidal silica solutionhaving a relatively high stability at relatively high pH. Exemplarycolloidal silicas can include the Ludox® HS, AS, SK, PW50, and PZ50available from W.R. Grace & Company, and can be gelled by increasing theion concentration by addition of salts and/or by changing the pH.According to this embodiment, TEA can first be added to the colloidalsilica, rendering a relatively stable colloidal silica solution. The pHof the solution may then be lowered by the addition of an acid, such ascitric acid, followed by thorough mixing and gel formation.

Exemplary compositions disclosed herein may further comprise an organicbinder. The addition of the organic binder component can furthercontribute to the cohesion and plasticity of the composition prior tofiring. This improved cohesion and plasticity can, for example, improvethe ability to shape the composition. This can be advantageous whenutilizing the composition to form skin coatings or when pluggingselected portions (such as the ends) of a honeycomb structural body.Exemplary organic binders include cellulose materials. Exemplarycellulose materials include cellulose ether binders such asmethylcellulose, hydroxypropyl methylcellulose, methylcellulosederivatives, and/or any combinations thereof. Particularly preferredexamples include methylcellulose and hydroxypropyl methylcellulose.Preferably, the organic binder can be present in the composition as asuper addition in an amount in the range of from 0.1 weight percent to5.0 weight percent of the inorganic powder batch composition, or even inan amount in the range of from 0.5 weight percent to 2.0 weight percentof the inorganic powder batch composition.

An exemplary liquid vehicle for providing a flowable or paste-likeconsistency to the disclosed compositions is water, although otherliquid vehicles can be used. To this end, the amount of the liquidvehicle component can vary in order to provide optimum handlingproperties and compatibility with the other components in the batchmixture. According to some embodiments, the liquid vehicle content ispresent as a super addition in an amount in the range of from 15% to 60%by weight of the inorganic powder batch composition, or even accordingto some embodiments can be in the range of from 20% to 50% by weight ofthe inorganic powder batch mixture. Minimization of liquid components inthe compositions can also lead to further reductions in the dryingshrinkage of the compositions during the drying process.

Exemplary compositions disclosed herein can optionally comprise one ormore processing aids such as a plasticizer, lubricant, surfactant,sintering aid, rheology modifier, thixotropic agent, dispersing agents,or pore former. An exemplary plasticizer for use in preparing theplugging composition is glycerine. An exemplary lubricant can be ahydrocarbon oil or tall oil. Exemplary commercially available lubricantsinclude Liga GS, available from Peter Greven Fett-Chemie and Durasyn®162 hydrocarbon oil available from Innovene. A commercially availablethixotropic agent is Benaqua 1000 available from Rheox, Inc. A poreformer, may also be optionally used to produce a desired porosity of theresulting ceramed composition. Exemplary and non-limiting pore formerscan include graphite, starch, polyethylene beads, and/or flour.Exemplary dispersing agents that can be used include the NuoSperse® 2000from Elementis and ZetaSperse® 1200, available from Air Products andChemicals, Inc.

In still other embodiments of the disclosed compositions, the gelationof colloidal silica can result in compositions having rheologicalproperties which may benefit from further modification. For example, thecompositions may be too thick for an intended use or may have low solidsloadings resulting in the formation of pinholes or shrinkage duringdrying. While such rheology can be desirable and advantageous in someapplications, the addition of a rheology modifier as noted above can beused to further control the rheology of the composition. To that end, insome embodiments, an exemplary rheology modifier is polyvinyl alcohol(PVOH). Both cold-water and hot-water soluble polyvinyl alcohol may beused. Compositions comprising polyvinyl alcohol can exhibit relativelylower viscosity at relatively higher solids loading, while stillpreventing the colloidal particles from migrating into micro-cracks ofthe honeycomb body on which the composition is applied. When used, thepolyvinyl alcohol can first be mixed with the colloidal silica and,optionally the ceramed refractory powder prior to the addition of thegelling agent. Compositions comprising the polyvinyl alcohol rheologymodifier enable gel formation but without the formation of a fullthree-dimensional gelled connectivity throughout the composition,resulting in a gelled state that flows relatively easily.

To prepare exemplary compositions as disclosed herein, the inorganicpowder batch mixture as described above can be mixed together with theorganic binder, followed by the incorporation of the liquid vehicle andinorganic binder components. As mentioned above, the inorganic bindercan be gelled either before or after having been introduced into thecomposition. If the inorganic binder is to be gelled prior to additionto the composition, the one or more gelling agents can be added to theinorganic binder, such as for example, a colloidal silica.Alternatively, if the inorganic binder is to be gelled after addition tothe powder composition, the one or more gelling agents can be introduceddirectly into the composition. Any optional processing aids can also beintroduced into the composition during or after the liquid addition.However, as noted above, if desired the rheology modifier, such aspolyvinyl alcohol can first be mixed with the inorganic binder and,optionally the refractory powder. Once the desired components arecombined, the composition can be thoroughly mixed to provide a flowablepaste-like consistency to the composition. In an exemplary embodiment,the mixing as described above can be done using a Littleford mixer or aTurbula mixer.

Once formed, the compositions disclosed herein can be applied to ahoneycomb body or structure defining a plurality of cell channelsbounded by cell channel walls. In exemplary embodiments, the wallthickness of each cell wall for the substrate can be, for example,between about 0.002 to about 0.010 inches (about 51 to about 254 μm).The cell density can be, for example, from about 100 to about 900 cellsper square inch (cpsi). In certain exemplary implementations, thecellular honeycomb structure can consist of multiplicity of parallelcell channels of generally square cross section formed into a honeycombstructure. Alternatively, other cross-sectional configurations may beused in the honeycomb structure as well, including rectangular, round,oblong, triangular, octagonal, hexagonal, or combinations thereof. Asused herein, “honeycomb” refers to the connected structure oflongitudinally-extending cells formed of cell walls, having a generallyrepeating pattern therein.

The honeycomb body can be formed from any conventional material suitablefor forming a honeycomb body. For example, in one embodiment, thehoneycomb body can be formed from a plasticized ceramic formingcomposition. Exemplary ceramic forming compositions can include thoseconventionally known for forming cordierite, aluminum titanate, siliconcarbide, aluminum oxide, zirconium oxide, zirconia, magnesium,stabilized zirconia, zirconia stabilized alumina, yttrium stabilizedzirconia, calcium stabilized zirconia, alumina, magnesium stabilizedalumina, calcium stabilized alumina, titania, silica, magnesia, niobia,ceria, vanadia, nitride, carbide, or any combination thereof.

The honeycomb body can be formed according to any conventional processsuitable for forming honeycomb monolith bodies. For example, in oneembodiment a plasticized ceramic forming batch composition can be shapedinto a green body by any known conventional ceramic forming process,such as, e.g., extrusion, injection molding, slip casting, centrifugalcasting, pressure casting, dry pressing, and the like. Typically, aceramic precursor batch composition comprises inorganic ceramic formingbatch component(s) capable of forming, for example, one or more of theceramic compositions set forth above, a liquid vehicle, a binder, andone or more optional processing aids including, for example,surfactants, sintering aids, plasticizers, lubricants, and/or a poreformer. In an exemplary embodiment, extrusion can be done using ahydraulic ram extrusion press, or a two stage de-airing single augerextruder, or a twin screw mixer with a die assembly attached to thedischarge end. In the latter, the proper screw elements are chosenaccording to material and other process conditions in order to build upsufficient pressure to force the batch material through the die. Onceformed, the green body can be fired under conditions effective toconvert the ceramic forming batch composition into a ceramiccomposition. Optimum firing conditions for firing the honeycomb greenbody will depend, at least in part, upon the particular ceramic formingbatch composition used to form the honeycomb green body.

In exemplary embodiments, the compositions disclosed herein can be usedas plugging material to plug selected channels of a honeycomb body inorder to form a wall flow filter. For example, in a honeycomb bodyhaving a plurality of cell channels bounded by porous cell channelwalls, at least a portion of the plurality of cell channels can compriseplugs, wherein the plugs are formed from a composition as disclosedherein. In some embodiments, a first portion of the plurality of cellchannels can comprise a plug sealed to the respective channel walls ator near the downstream outlet end to form inlet cell channels. A secondportion of the plurality of cell channels can also comprise a plugsealed to the respective channel walls at or near the upstream inlet endto form outlet cell channels. Other configurations having only one endplugged, as well as partially plugged configurations (having someunplugged channels) are also contemplated.

In other embodiments, the disclosed compositions are suitable for use informing an after-applied surface coating or skin on a peripheral regionof a honeycomb body or structure. In still other embodiments, disclosedcompositions can be applied as a segment cement in order to join two ormore honeycomb bodies or segments of honeycomb bodies together.

Once the composition has been applied to a honeycomb structure in amanner as described herein, the composition can be optionally driedand/or fired. The optional drying step can comprise first heating thecomposition at a temperature and for a period of time sufficient to atleast substantially remove any liquid vehicle that may be present in thecomposition. As used herein, at least substantially removing any liquidvehicle includes the removal of at least 95%, at least 98%, at least99%, or even at least 99.9% of the liquid vehicle present in thecomposition prior to firing. Exemplary and non-limiting dryingconditions suitable for removing the liquid vehicle include heating thecomposition at a temperature of at least 50° C., at least 60° C., atleast 70° C., at least 80° C., at least 90° C., at least 100° C., atleast 110° C., at least 120° C., at least 130° C., at least 140° C., oreven at least 150° C. In one embodiment, the conditions effective to atleast substantially remove the liquid vehicle comprise heating thecomposition at a temperature in the range of from 60° C. to 120° C.Further, the heating can be provided by any conventionally known method,including for example, hot air drying, RF and/or microwave drying.

The optional firing step can include conditions suitable for convertingthe composition to a primary crystalline phase ceramic compositioninclude heating the honeycomb with applied composition to a peaktemperature of greater than 800° C., 900° C., and even greater than1000° C. A ramp rate of about 120° C./hr during heating may be used,followed by a hold at the peak temperature for a temperature of about 3hours, followed by cooling at about 240° C./hr.

Compositions disclosed herein can include those that set at atemperature of less than 200° C., such as a temperature of less than100° C., and further such as a temperature of less than 50° C.,including compositions that can be used in plugging processes employing“cold set” plugs. In cold set plugging, only drying of the pluggingmixture is required to form a seal between the plugs and the channelwalls of the honeycombs. When a cold set plugging process is employed,heating of the plugged honeycombs to temperatures in the 35-110° C.range can be useful to accelerate drying. In some cold set pluggingprocesses, it is anticipated that final plug consolidation, includingthe removal of residual temporary binder bi-products and strengtheningof the seals, can occur in the course of subsequent processing steps(e.g., in the course of catalyzation or canning) or during first use(e.g., in an exhaust system).

For example, exemplary compositions in which cold set plugging may beemployed include those comprising a refractory filler that comprises atleast one inorganic powder, such as at least one of aluminum titanateand cordierite, the inorganic powder having a median particle size (D₅₀)of from 15 to 50 microns, such as from 30 to 40 microns, and a gelledinorganic binder, such as gelled colloidal silica. At least one gellingagent, such as at least one of hydrochloric acid, sulfuric acid, nitricacid, citric acid, and acetic acid, ammonium hydroxide, sodiumhydroxide, and triethanol amine (hereinafter “TEA”) may be added eitherbefore (e.g., as a pre-mix with the gelled inorganic binder) or duringbatching in order to gel the inorganic binder. Such compositions canprovide plugs that set in a porous ceramic honeycomb body (and bethereby permanently sealed to the channel walls) at a temperature ofless than 200° C., such as less than 100° C., and further such as lessthan 50° C., including about 25° C. Such plugs can each have a push outstrength of at least 10 bar.

The disclosure and scope of the appended claims will be furtherclarified by the following example.

EXAMPLES

A plugging composition according to embodiments disclosed herein (E1) aswell as a comparative plugging composition (C1) were prepared andapplied to the outlet channels of a honeycomb body, which was the sameas a honeycomb body used to make a Corning® DuraTrap® aluminum titanate(AT) filter having 300 cells per square inch, 12 mil thick walls, andasymmetric cell technology (ACT), wherein the honeycomb body had adiameter of about 6.4 inches and an axial length of about 5.5 inches.Following application, the plugs were dried and then fired for about 3hours at about 1,000° C. The components of the plugging compositions areset forth in Table 1 below.

TABLE 1 Component C1(wt %) E1(wt %) Aluminum titanate powder 63.6 — D₅₀= 21 μm, D₁₀ = 7 μm, D₉₀ = 55 μm Aluminum titanate powder — 64.6 D₅₀ =35 μm, D₁₀ = 10 μm, D₉₀ = 92 μm Colloidal Silica (Ludox ® 19.9 20.1HS-40) Methylcellulose 0.5 0.5 (Methocel ® F240) Water 12.2 10.9 CitricAcid 0.5 0.5 Triethanol amine (TEA) 3.3 3.4

FIG. 1 shows the average plug depth and depth range of plugs applied tothe honeycomb from C1 and FIG. 2 shows the average plug depth and depthrange of plugs applied to the honeycomb from E1. As can be seen fromFIGS. 1 and 2, plugs applied from E1 had a shorter average plug depth(5.811 millimeters) than plugs applied from C1 (7.600 millimeters).Plugs applied from E1 also had a smaller depth range (1.07 millimeters)than plugs applied from C1 (2.46 millimeters). Accordingly, plugsapplied from E1 had a depth range that was 18.4% of their average plugdepth while plugs applied from C1 had a depth range that was 32.4% oftheir average plug depth.

Although not intended to be bound by theory, the inventors discoveredfriable plug centers according to exemplary embodiments caused bymigration of the inorganic binder during the drying process. The friableplug centers lead to visual inconsistencies in sectioned plugs andpossible reduced resistance to air erosion in the event that a plug isdamaged. One method of minimizing binder migration may be to gel thebinder. Manipulation of the drying conditions was conducted to affectsome change to the appearance and erosion resistance of the plugcenters, as well.

The inventors found the surprising result that involved the use of apoly disperse colloidal silica as the inorganic binder in the cold setplugs. This use of poly disperse colloidal silica as the inorganicbinder was coupled with a reduced organic binder level, coupled with alower water demand that enabled better particle packing in the cold setplug composition, and a denser cold set plug composition. Althoughpre-gelling the colloidal silica may be desirable under some conditions,it was not necessary. This poly disperse particle size distribution ofthe colloidal silica minimized binder migration, improved visualappearance in cross section, improved air erosion resistance byminimizing or eliminating the friable core, enhanced the process windowenabling more inorganic binder, less organic binder and expanded thedrying window of the cold set plug cement over other cold set plugcompositions.

With the non-gelled inorganic binder in the cold set pluggingcomposition, it was also found, according to certain exemplaryembodiments that the refractory filler may include inorganic powderhaving a further reduced median particle size with improved results. Forexample, the refractory filler may include at least one inorganic powderhaving a median particle size (D₅₀) of at least 10 microns, such as amedian particle size (D₅₀) of from 10 to 50 microns, and further such asa median particle size (D₅₀) of from 15 to 40 microns.

Experiments were conducted on Examples S1 and S2 of exemplaryembodiments of the cold set cement compositions disclosed herein. Theexperimental compositions were prepared according to Table 2 and appliedto the channels of a cordierite honeycomb body. The cordierite honeycombbody had 200 cells per square inch, 12 mil thick walls, the honeycombbody had a diameter of about 12 inches and an axial length of about 9inches.

TABLE 2 Component S1 (wt %) S2 (wt %) Coarse Cordierite powder 64 64Colloidal Silica 24 — (Ludox ® HS-40) Colloidal Silica — 19.18 (Ludox ®PW50 EC) Methylcellulose 1.19 1.19 (Methocel ® A4M) Water 11.28 16

Following initial plant trials, data was collected on plug samples ofExample S1 composition. Upon examining the collected data it wasdiscovered that the interior of plugs of Example S1 composition were nothomogenous. During assessment of the plugs, plug faces were calcined for3 hrs at 600° C. to evaluate the plugs in a “worst case” condition thatthey might experience after downstream processing or in-service. Thecalcination is not necessarily part of the production process. Calcinedcross sections of Example S1 composition show that the plugs generallyhave two different regions: a relatively hard outer shell and a softer,more friable core. FIG. 3 shows plugs of Example S1 composition in thehoneycomb body after calcination, sectioning, and subjecting the exposedcold set plug cement to pressurized air erosion testing. Example S1composition plug cement uses Ludox® HS-40, a colloidal silica having anarrow particle size distribution centered at approximately 12 nm, asthe inorganic binder.

The inventors postulate that the very small silica particles in Ludox®HS-40 may be free to travel with the water during the drying processtoward the outer edges. Thus, the very small silica particles end upconcentrated at the outer edges of the plug and form the hard shell. Thesilica migration hypothesis was corroborated by a silica scan done bymicroprobe analysis as shown in FIG. 4. The red/yellow color in the leftimage indicates higher silica concentration. The microprobe silica scanshowed higher silica concentrations in and around the edges than in thecenter of an Example S1 composition plug without calcination.

To address the silica migration issue, a study was undertaken. As aresult, a change was made from the small silica particle size Ludox®HS-40 to Ludox® PW50EC, a polydisperse colloidal silica with a muchbroader particle size range. Ludox® PW50EC has a particle size range D₅₀of approximately 10-100 nm particle size distribution (PSD) as comparedto about 12 nm D₅₀ in Ludox® HS-40. In theory, the larger particles ofLudox® PW50EC do not migrate as easily leaving them dispersed and in thecenter of the plug. The smallest of the particles in the Ludox® PW50ECare still able to migrate and bind the plug to the cell wall.

FIG. 5A shows a transmission electron microscopy image (250,000×) of themono-modal disperse colloidal silica with a particle size range D₅₀ ofapproximately 12 nm. FIG. 5B shows a transmission electron microscopyimage (200,000×) of the colloidal silica having a poly-disperse mixtureof larger particle size range D₅₀ of approximately 70 nm and smallerparticle size range D₅₀ of approximately 12 nm.

Table 3 shows the particle size distribution (PSD), surface area, wt %silica for Examples S1-S15 studied. These Examples were prepared asdescribed above except for the different colloidal silicas as indicatedin Table 3. For each Example the results of cross section, erosion, plugdepth, and plug strength testing as described herein are presented. Forthe cross section, erosion, plug depth, and plug strength a thresholdwas established as a performance indicator. The letter ‘A’ indicates theExample performed at or above this threshold. The letter ‘B’ indicatesthe Example performed below this threshold. Table 3 also includes theproduct and supplier of the silica used in each Example S1-S15. Due tovariation in each product from the supplier, the particle sizedistribution (PSD) is presented as the typical PSD in Table 3 as is theSurface Area in square meters per gram (m²/g) and weight percent (wt %)silica. In Example S5, the silica content of the product was too low toachieve a plugging composition denoted by the letter ‘C’.

As can be seen by the results in Table 3, the polydisperse colloidalsilica Example S2 outperformed the monomodal fine colloidal silicaExample S1. Further Examples S3, S4, and S5 also performed below thethreshold denoted by ‘B’ in Table 3. However, Examples S6-S15 performedat or above the threshold denoted by ‘A’ in Table 3.

FIGS. 6A and 6B show the relationship between particle size distribution(PSD) and surface area for colloidal silicas in Examples S1-S15. Thesurface area specification tightly limits possible PSD range. The Ludox®PW50EC, Example S2, produced superior results based on specified SurfaceArea limits as illustrated in FIGS. 6A and 6B.

TABLE 3 Surface Example PSD Area Silica Cross Plug Plug No. Product (nm)(m²/g) wt % Section Erosion Depth Strength S1 HS-40 by 12 228 40 B B B AGRACE S2 PW-50 by 55 75 50 A A A A GRACE S3 Snowtex ST-40 15 191 40.5 BB B A by NISSAN S4 1142 by 15 200 40 B B B A NALCO S5 Snowtex ST- 35 10220.5 C C C C 20L by NISSAN S6 IDISIL SI-1540 15 191 40 A A A A by EVONIKDEGUSSA S7 1050 by 20 150 50 A A A A NALCO S8 TM-50 by 22 130 50 A A A AGRACE S9 Snowtex ST-50 25 141 48 A A A A by NISSAN S10 IDISIL EM- 35 10230 A A A A 3530K by EVONIK DEGUSSA S11 IDISIL SI-4540 45 73 40 A A A Aby EVONIK DEGUSSA S12 IDISIL SI-5530 55 54 30 A A A A by EVONIK DEGUSSAS13 1060 by 60 50 50 A A A A NALCO S14 2329 by 75 40 40 A A A A NALCOS15 Snowtex ST- 85 35 40.5 A A A A ZL by NISSAN

A range of organic and inorganic binder (colloidal silica) levels wereinvestigated. Samples having 25, 30 and 35 wt % poly-disperse colloidalsilica (Ludox® PW50EC) super addition were made with 1, 1.5, 2, 2.5, and3 wt % methylcellulose (Methocel® A4M) super addition. It was discoveredthat the poly-disperse colloidal silica enables higher inorganic binderlevels and lower organic binder levels as compared to compositionscomprising the mono-modal disperse colloidal silica, for example, as inExample S1. A similar investigation was performed with compositionscomprising the mono-modal disperse colloidal silica (Ludox® HS-40) onproduction equipment. It was found that higher levels of mono-modaldisperse colloidal silica compositions lead to higher pressures andleaking seals of the production equipment. Thus, mono-modal dispersecolloidal silica compositions were deemed to be less desirable from aproduction process standpoint.

From plug depth measurements on parts plugged with a deep cement dam(i.e., enough cement to make very long plugs, for example greater thanabout 10 to 12 mm), it was found that poly-disperse colloidal silicaenables deep plugs at reduced methylcellulose levels. For example,mono-modal disperse colloidal silica requires about 2.5 wt %methylcellulose at 25 wt % mono-modal disperse colloidal silica toachieve acceptable plug depths. FIG. 7 shows a plot of plug depth ofcompositions according to exemplary embodiments. In this study, only the25 wt % poly-disperse colloidal silica at the lowest organic binderlevel did not achieve a deep plug depth. The 30 wt % poly-dispersecolloidal silica at the lowest organic level achieved an acceptable plugdepth, although being borderline. As evident from FIG. 7, moremono-modal disperse colloidal silica makes the plug cement rheologyworse (limits plug depth) while increased poly-disperse colloidal silicaimproves plug cement rheology (enables deep plug depth capability atlower methylcellulose levels).

Air erosion testing is a simple lab test done on calcined parts (heattreated at 600° C. for 3 hours) to mimic the ash cleaning process that aparticulate filter (PF), for example, a diesel particulate filter (DPF),may undergo during its lifetime. The plug face was sliced in half toexpose the center of the plugs. For example, FIG. 3 shows the centers ofthe plugs is the area of the cold set cement having the mono-modaldisperse colloidal silica composition where friability was observed. Thelowest pressure tested was 30 psi and the maximum was 130 psi. Productsthat performed above the threshold were those that passed 130 psi. Theair erosion testing results are plotted in a graph shown in FIG. 8. TheApplicants observed that the organic binder level contributed to theplug center friability. Therefore, achieving an acceptable plug cementrheology to produce deep plug depths while lowering the amount oforganics is beneficial to reducing the friability of the centers of theplugs. The poly-disperse colloidal silica improves plug cementcomposition to enable deep plug depths while lowering the amount oforganics to reduce the friability of the centers of the plugs.

Plug pushout testing was performed to determine plug adherence to thecell wall (plug strength) by utilizing a load cell to push on the plugwith a square pin from the bottom of the plug. The plug depth wasmeasured and then the force required to break through the plug andremove it from the honeycomb body face was recorded.

The plug pushout testing results are graphically plotted as illustratedin FIG. 9. From the plug pushout results shown in FIG. 9, it can be seenthat increased levels of poly-disperse colloidal silica improves plugcement composition to dampen the effect of organic binder level on plugstrength. For example, at the 25 wt % level of poly-disperse colloidalsilica, the pushout strength per mm plug depth of calcined pluggedhoneycomb structure decreases with an increase in methylcelluloseorganic binder. In contrast, at the 30 and 35 wt % level ofpoly-disperse colloidal silica, the pushout strength per mm plug depthof calcined plugged honeycomb structure hardly decreases with anincrease from 1 to 3 wt % methylcellulose organic binder.

FIG. 10 shows a microprobe silica scan of a cross sectioned plug appliedto a honeycomb structure according to an exemplary embodiment. Themicroprobe silica scan illustrates a much more uniform distribution ofsilica across the plug comprising poly-disperse colloidal silica thanthe distribution of silica across the plug comprising mono-modaldisperse colloidal silica. FIG. 10 indicates less silica migrationoccurred during drying of the plug comprising poly-disperse colloidalsilica than during drying of the plug comprising mono-modal dispersecolloidal silica. The yellow/red color in the microprobe image of FIG.10 indicates silica concentration in the plug comprising the cold setcement having poly-disperse colloidal silica. The microprobe image ofFIG. 10 indicates silica is much more evenly dispersed through the plugthan in the microprobe image of FIG. 4 for the plug comprising the coldset cement having mono-modal disperse colloidal silica.

Additionally, the Applicants found that increasing batch density byremoving organic binder and increasing colloidal silica levels impededsilica migration by decreasing the size of channels between particles,that is, better particle packing was achieved in the cold set cementplugs comprising the poly-disperse colloidal silica. A comparison of thedensity of the cement plugs confirmed the closer particle packing in thecement plugs comprising the poly-disperse colloidal silica. The densityof the cement plugs comprising the poly-disperse colloidal silica isabout 6% greater than the density of the cement plugs comprising themono-modal disperse colloidal silica. Another unexpected benefit ofusing the poly-disperse colloidal silica in the cold set cement is thatreducing the organic binder means less water was needed in the cement.Table 4 shows the average density of seven exemplary embodiments of coldset cement batches having the mono-modal disperse colloidal silica andthe average density of eight exemplary embodiments of cold set cementbatches having the poly-disperse colloidal silica mixed in the lab.

TABLE 4 Cold set cement composition Density (g/mL) Number of batchesmono-modal disperse 1.46 7 colloidal silica poly-disperse colloidal 1.558 silica

FIG. 11 shows a plot of plug density according to exemplary embodimentsof plug composition. The densities of the examples plotted in FIGS. 8and 9 are shown in FIG. 11. As the amount of organic binder is decreaseddue to the improved rheological properties resulting from thepoly-disperse colloidal silica, the graph in FIG. 11 illustrates thatthe density increases. In addition, for the same amount ofmethylcellulose in the batch composition, the cold set cement plugdensity increases when the amount of poly-disperse colloidal silica isincreased as shown in FIG. 11.

Samples according to exemplary embodiments of the disclosed compositionwere prepared as set forth in Table 2 (above) to make Example S1 andExample S2 cold set cement compositions. The same wt % cordierite(solids loading) was used in Examples S1 and S2, with the onlydifference being the Ludox® type (amounts are adjusted to account forthe difference in percent silica in the two types of Ludox®). FIG. 12shows Example S1 and S2 compositions of cold set cement plugs introducedin honeycomb body cells, dried, and sectioned. The sectioned plugs werethen subjected to pressurized air at 130 psi. FIG. 12 shows sectionedExample S1 plugs after hot air drying (HAD) at (a) and after microwavedrying at (b). The sectioned Example S1 plugs hot air dried (a) andmicrowave dried (b) exhibited a friable center. FIG. 12 shows sectionedExample S2 plugs after hot air drying (HAD) at (c) and after microwavedrying (MW) at (d). As can be seen from comparing the photographs ofsectioned plugs of Example S1 (a) and Example S2 (c) in FIG. 12, thepolydisperse colloidal silica eliminates the appearance of a friablecenter when plugs were hot air dried. Comparing the photographs ofsectioned plugs of Example S1 (b) and Example S2 (d) in FIG. 12, thepolydisperse colloidal silica minimizes the appearance of a friablecenter when plugs were microwave dried.

FIG. 13 shows cutback erosion results of exemplary embodiments of thedisclosed compositions. In the cutback erosion tests, plugs of theExample S2 composition comprising the polydisperse colloidal silicademonstrated a substantially higher cutback erosion pressure compared tothe plugs of the Example S1 composition comprising the mono-modaldisperse colloidal silica. FIG. 14 shows plug push out test results ofexemplary embodiments of the disclosed compositions. The use ofpolydisperse colloidal silica according to exemplary embodimentsdisclosed herein improved the visual appearance of the sectioned coldset plug cement and minimized the friable nature of the center of theplug as illustrated by the cutback erosion results. Additionally, thepolydisperse colloidal silica of the Example S2 plug cement compositiondoes not adversely affect the plug cement adherence to the honeycombcell wall as shown in the plug pushout results of FIG. 14.

According to exemplary embodiments of the disclosure the polydispersecolloidal silica inorganic binder may have a first particle sizedistribution and a second particle size distribution greater than thefirst particle size distribution. The first particle size distributionand the second particle size distribution may partially overlap so thatfor the purposes of this disclosure, a first distribution may beunderstood to have a first peak or first set of peaks and the secondparticle size distribution may have a second peak or second set ofpeaks. In the instance of sets of peaks, the uppermost peak of the firstset would be the most adjacent peak to the lower most of the second setand perhaps even partially overlapping.

For example, in one set of exemplary embodiments, the first particlesize distribution has a median particle size (D₅₀) of at least 10 nm,such as a median particle size of (D₅₀) of from 10 to 50 nm, and furthersuch as a median particle size (D₅₀) of from 10 to 40 nm, such as amedian particle size (D₅₀) of from 10 to 25 nm, and even further such asa median particle size (D₅₀) of from 15 to 35 nm, and yet even furthersuch as a median particle size (D₅₀) of from 20 to 35 nm. As a furtherexample, in one set of exemplary embodiments, the first particle sizedistribution has a median particle size (D₅₀) of less than 20 nm, suchas a median particle size of (D₅₀) of less than 25 nm.

In one set of exemplary embodiments, the second particle sizedistribution has a median particle size (D₅₀) of at least 40 nm, such asa median particle size of (D₅₀) of from 40 to 300 nm, such as a medianparticle size of (D₅₀) of from 40 to 100 nm, and further such as amedian particle size (D₅₀) of from 50 to 250 nm, and even further suchas a median particle size (D₅₀) of from 60 to 100 nm, and yet evenfurther such as a median particle size (D₅₀) of from 50 to 95 nm.

For example, the polydisperse colloidal silica inorganic binder mayinclude any combination of these first particle size distributions andsecond particle size distributions, for example, the first particle sizedistribution has a median particle size (D₅₀) of from 10 to 25 nm andthe second particle size distribution has a median particle size (D₅₀)of from 40 to 100 nm.

According to exemplary embodiments of the disclosure the first particlesize distribution and the second particle size distribution mayconstitute greater than 35 wt % of the polydisperse colloidal silicainorganic binder particles. For example, in one set of exemplaryembodiments, the first particle size distribution and the secondparticle size distribution may constitute greater than 40 wt % of thepolydisperse colloidal silica particles, such as greater than 50 wt %,such as greater than 60 wt %, and further such as greater than 70 wt %,and even further such as greater than 80 wt % and yet even further suchas greater than 90 wt %.

Unless otherwise expressly stated, it is in no way intended that anymethod set forth herein be construed as requiring that its steps beperformed in a specific order. Accordingly, where a method claim doesnot actually recite an order to be followed by its steps or it is nototherwise specifically stated in the claims or descriptions that thesteps are to be limited to a specific order, it is no way intended thatany particular order be inferred.

It will be apparent to those skilled in the art that variousmodifications and variations can be made without departing from thespirit or scope of the invention as set forth in the appended claims.Since modifications combinations, sub-combinations and variations of thedisclosed embodiments incorporating the spirit and substance of thedisclosure may occur to persons skilled in the art, the disclosureshould be construed to include everything within the scope of theappended claims and their equivalents.

What is claimed is:
 1. A composition for applying to a honeycomb bodyhaving a plurality of parallel channels, the composition comprising: arefractory filler having a particle size distribution; an organicbinder; an inorganic binder; and a liquid vehicle; wherein the inorganicbinder comprises a polydisperse colloidal silica.
 2. The composition ofclaim 1, wherein the refractory filler comprises at least one inorganicpowder selected from the group consisting of cordierite, mullite,aluminum titanate, silicon carbide, silicon nitride, calcium aluminate,beta-eucryptite, and beta-spodumene.
 3. The composition of claim 2,wherein the refractory filler has a median particle size (D₅₀) of from10 to 50 microns.
 4. The composition of claim 1, wherein thepolydisperse colloidal silica comprises a surface area of less than orequal to about 150 m²/g.
 5. The composition of claim 1, wherein thecomposition sets at a temperature of less than 200° C.
 6. Thecomposition of claim 1, wherein the inorganic binder comprisesnon-gelled colloidal silica.
 7. The composition of claim 1, wherein thepolydisperse colloidal silica consists of a disperse colloidal silicacomprising a first particle size distribution and a second particle sizedistribution greater than the first particle size distribution.
 8. Thecomposition of claim 7, wherein the first particle size distributioncomprises a D₅₀ of greater than about 10 nm and less than about 40 nmand the second particle size distribution comprises a D₅₀ of greaterthan about 40 nm and less than about 300 nm.
 9. The composition of claim8, wherein at least 15 wt % of the first particle size distributioncomprises a D₅₀ of no greater than about 25 nm and at least 15 wt % ofthe second particle size distribution comprises a D₅₀ of no less thanabout 50 nm.
 10. The composition of claim 8, wherein the weight percentof the first particle size distribution and the second particle sizedistribution constitutes greater than 35 wt % of the particles in thepolydisperse colloidal silica.
 11. A porous ceramic honeycomb bodycomprising a plurality of parallel channels bounded by porous ceramicchannel walls, wherein selected channels incorporate plugs permanentlysealed to the channel walls, wherein the plugs comprise a refractoryfiller having a particle size distribution and an inorganic binder andwherein the inorganic binder comprises a polydisperse colloidal silica.12. The porous ceramic honeycomb body of claim 11, wherein therefractory filler comprises at least one inorganic powder selected fromthe group consisting of cordierite, mullite, aluminum titanate, siliconcarbide, silicon nitride, calcium aluminate, beta-eucryptite, andbeta-spodumene.
 13. The porous ceramic honeycomb body of claim 11,wherein the plugs set at a temperature of less than 200° C.
 14. Thecomposition of claim 11, wherein the polydisperse colloidal silicacomprises a surface area of less than or equal to about 150 m²/g. 15.The porous ceramic honeycomb body of claim 11, wherein the polydispersecolloidal silica consists of a disperse colloidal silica comprising afirst particle size distribution and a second particle size distributiongreater than the first particle size distribution.
 16. The porousceramic honeycomb body of claim 15, wherein the first particle sizedistribution comprises a D₅₀ of about 10 nm and less than about 40 nmand the second particle size distribution comprises a D₅₀ of greaterthan about 40 nm and less than about 300 nm.
 17. A method for applying aplugging composition to a honeycomb body having a plurality of parallelchannels, the method comprising: applying to the honeycomb body, acomposition comprising: a refractory filler having a particle sizedistribution; an organic binder; an inorganic binder; and a liquidvehicle; wherein the inorganic binder comprises a polydisperse colloidalsilica.
 18. The method of claim 17, further comprising setting thecomposition at a temperature of less than 200° C.
 19. The method ofclaim 17, wherein the polydisperse colloidal silica consists of adisperse colloidal silica comprising a first particle size distributioncomprising a D₅₀ of less than about 25 nm and a second particle sizedistribution greater comprising a D₅₀ of greater than about 40 nm. 20.The method of claim 17, wherein the polydisperse colloidal silicacomprises a surface area of less than or equal to about 150 m²/g.